CN1041376A - Improve the composition of cationic electrodepositable with thionamic acid and derivative thereof - Google Patents
Improve the composition of cationic electrodepositable with thionamic acid and derivative thereof Download PDFInfo
- Publication number
- CN1041376A CN1041376A CN89106745A CN89106745A CN1041376A CN 1041376 A CN1041376 A CN 1041376A CN 89106745 A CN89106745 A CN 89106745A CN 89106745 A CN89106745 A CN 89106745A CN 1041376 A CN1041376 A CN 1041376A
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- Prior art keywords
- composition
- resin
- acid
- electrodeposition
- mutually
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- 239000000203 mixture Substances 0.000 title claims abstract description 107
- 239000002253 acid Substances 0.000 title claims abstract description 54
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 35
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- 239000011347 resin Substances 0.000 claims abstract description 78
- 238000004070 electrodeposition Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 29
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 24
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- 239000004593 Epoxy Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
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- 239000006185 dispersion Substances 0.000 abstract description 39
- 230000007935 neutral effect Effects 0.000 abstract description 15
- 238000002161 passivation Methods 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 60
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/901—Electrodepositable compositions
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Detergent Compositions (AREA)
Abstract
A kind of electrodepositable composition that contains the resin phase that is dispersed in the water medium is now disclosed.This resin have mutually to small part through thionamic acid or derivatives thereof neutral basic nitrogen group, this sour molecular formula is as follows:
R is H or C in the formula
1-C
4Alkyl.Said composition exists with smaller particulate aqueous dispersions form, when it is used for the cationic electrodeposition process, can form the thick film with high throwing power.In addition, but use also passivation anode of thionamic acid.
Description
The present invention relates to the composition of cationic electrodepositable and in the cationic electrodeposition method, use these compositions.
As the galvanic deposit of coated application method, promptly be under the effect of applying electrical potential, to make the film-forming composition deposition.Galvanic deposit has been increasingly important in coated industry, because its more non-electrophoretic coating method has higher industrial utilization, the superiority of erosion resistance and lower environmental pollution significantly.At first, galvanic deposit is to carry out under as the anodic situation waiting to be coated with workpiece, and this galvanic deposit is referred to as the anionic electrodeposition deposition.Yet in 1972, cationic electrodeposition was introduced into market.Cationic electrodeposition obtains to popularize steadily since then, and it has become most popular method in galvanic deposit now.The Motor vehicles sum of produced worldwide is to adopt cationic electrodeposition to provide primer coating more than 80 percent now.
Be used for the coating composition preparation of cationic electrodeposition process, the resin glue that contains basic group (for example basic nitrogen group) is through a kind of acid neutralization.The resin cation (R.C.) that is generated is scattered in the water, combines to generate coating with pigment and some other additive that is generally used in the cationic electrodeposition process.Typically neutralizing with acid is some organic acids, and for example, acetic acid and lactic acid are because these acid can provide very even and stable dispersion.Although know the use mineral acid, for example nitric acid, sulfuric acid and phosphoric acid also can be used as the neutralizing agent in the cationic electrodeposition process, and these acid generally can not provide gratifying dispersion for the cationic electrodeposition process of industry.
Have now found that according to the present invention, thionamic acid can be used as the neutralizing agent of positively charged ion coating composition.Formed dispersion liquid has tiny and homogeneous granules, makes dispersion liquid strengthen the stability of self owing to reduce sedimentation; And the product of acquisition cleaning.In addition, along with improving throwing power, the coating composition of cationic electrodeposition can deposit becomes thicker coating.Making us somewhat surprised is, thionamic acid can make anode passivation, thus the corrosion of opposing anolyte, the cationic electrodeposition composition association that this anolyte neutralize with classic organic acid (for example lactic acid and acetic acid) usually.
People such as Deinega are at a Russian document " colloid magazine " (the 7-8 month in 1975), and the 37th volume the 4th phase, is published papers on the 691-695 page or leaf: " cathode codeposition of metal and polymkeric substance ".Article has disclosed the electrochemical preparation of metal-polymer coating.The available cationic melamine-formaldehyde resin of this coating composition itself, aniline-formaldehyde resin and urea-formaldehyde resins preparation.Mention in the explanation of this article 692 page tables 2 and Fig. 3 that thionamic acid lead can use to form electrodeposition bath with the positively charged ion aniline-formaldehyde resin.Yet content plumbous in the bath is very high, that is: lead content is approximately 70,000～120 in the bath that relates in the table 2,000ppm, and lead content is approximately 10,000～150 in the bath that relates among Fig. 3,000ppm.PH value during these are bathed is very low, is approximately 1～2.
The composition that the present invention relates to has low-down lead content, typically less than 2, and 000ppm, and higher pH value is arranged, be generally 5～8.Composition of the present invention mainly provides organic coating, wherein contain a small amount of lead from pigment or other source, and the composition of mentioning in the above-mentioned Russian document provides the coating of the organo-metallic with high lead content.
United States Patent (USP) 4,724,244 disclose the cationic electrodeposition resin that contains basic nitrogen group and sulfonic acid group.Such resin can obtain by resin and the thionamic acid reaction that contains primary amine and secondary amine group.This reaction takes place by ammonolysis reaction, that is,
Therefore, thionamic acid does not resemble in the present invention is as neutralizing agent.In fact United States Patent (USP) 4,724, and 244 disclose typical organic acid as lactic acid or acetic acid as neutralizing agent.
According to the present invention, can provide a kind of composition that contains the resin phase cationic electrodepositable that is dispersed in the water medium.The pH value of this composition is at least 5, is generally 5-8, and it contains less than 2, the lead of 000ppm.Resin has the basic nitrogen group mutually, and this group to the acid with following formula of small part neutralizes:
Wherein R is H or C
1-C
4Alkyl.
The acid of using in preparation electrodeposition composition of the present invention is thionamic acid and derivative thereof, and these sour structural formulas are:
Wherein R is H or C
1-C
4Alkyl.Acid preferably is thionamic acid itself.When mentioning " thionamic acid ", mean the sulfamic acid derivatives of being not only thionamic acid itself and also referring to said structure later on.
This thionamic acid is used at least in part neutralizing and contains the resin of basic group (for example basic nitrogen group), that is:
This neutralization reaction takes place under comparatively gentle condition, is typically between about 20 ℃～100 ℃ to take place.This reaction is under agitation condition thionamic acid to be added in the resin, again will be the neutral resin dispersion in water medium.Or under agitation condition, resin is added in the thionamic acid solution lentamente to form dispersion liquid.A kind of dispersive method in back is more better, the homogeneous granules because it can produce more tiny.This paper " neutralization reaction " described later also comprises " part neutralization reaction ".
The neutral degree depends on which kind of resin related be.In general, the consumption of thionamic acid is preferably 6-7 for can make the pH value of electrodepositable composition be typically 5-8.Resin will migrate to negative electrode and galvanic deposit on negative electrode mutually under the voltage influence that is applied in electrodeposition process.Typical degree of neutralization is 30% of premier's opinion neutralization equivalent at least.
Except thionamic acid, also can use thionamic acid and other acid () mixture for example: acetic acid, lactic acid and dimethylol propionic acid.When using mixture, thionamic acid generally accounts at least and neutralizes with 30% of sour gross weight.
With thionamic acid neutral resin be main film-forming resin in the electrodepositable composition.The example of this class film-forming resin is resin and the primary amine that contains epoxy group(ing), and secondary amine is (for example in United States Patent (USP) 3,663,389; 3,984,299; 3,947,338 and 3,947, described in 339) reaction product.Usually, 1 of epoxy-containing yl resin, 2-epoxy group(ing) valency be greater than 1, is preferably the polyglycidyl ether of polyphenol [for example 4,4 '-two (hydroxyphenyl) propane].Other example comprises the polyglycidyl ether of (line style) phenolic varnish type phenolic condensation compound and the glycidyl acrylate multipolymer with glycidyl methacrylate.
These resins use in the lump with end capped polyisocyanate curing agent usually.This polymeric polyisocyanate can be by above mentioned United States Patent (USP) 3,984,299 described such whole end-blockings, perhaps United States Patent (USP) 3,947,338 described such isocyanate moiety ground end-blockings and react with resin backbone as the aforementioned.Except that end capped polyisocyanate curing agent, also can use at Europe patent application No.12 the fat group-transfer solidifying agent described in 463.Also can use in U.S. Patent No. 4,134 the cationic electrodeposition composition described in 932 from the mannich base preparation.In U.S. Patent No. 4,134,866 and DE-OSNo.2, the single-component composition described in 707,405 also can be used as film-forming resin.Except that the epoxy amine reaction product, film-forming resin also can be selected from amino-contained acrylic copolymer (for example in U.S. Patent No. 3,455,806 and 3,928, those multipolymers described in 157).
Resin is those resins that contain primary amine and/or secondary amine preferably.Such resin is in U.S. Patent No. 3,663,389; The existing description in 3,947,339 and 4,116,900.At United States Patent (USP) 3,947, in 339, the multi-ketimine derivative of polyamines (for example diethylenetriamine or Triethylenetetramine (TETA)) and the resin reaction that contains the epoxidation base.When reaction product neutralizes with thionamic acid and makes it be dispersed in the water, just generated the free primary amine group.Equally, when polyepoxide and the reaction of excessive polyamines (for example diethylenetriamine and Triethylenetetramine (TETA)), can generate normal product, and remaining polyamines can vacuum extract from reaction mixture.United States Patent (USP) 3,663,389 and 4,116,900 have described this class product.
This cation composition in water of the present invention exists with the dispersion of water." dispersion " speech it is believed that two-phase-transparent, translucent or opaque resin system, resin wherein as disperse phase and water as external phase.The average particle size particle size of resin phase is generally less than 10 microns, usually less than 5 microns, is preferably less than 0.5 micron.Dispersion liquid of the present invention is littler than the particle size of the similar dispersion liquid for preparing with typical organic acid (for example lactic acid and acetic acid).This thinner particle size can provide better dispersion stabilization.
The concentration of resin in water medium is 1% of aqueous dispersions weight usually at least, generally approximately from 2% to 60%.When composition of the present invention calculated with the resin conc forms, the content of resin solid generally accounted for about 26%～60% of aqueous dispersions weight.When composition of the present invention calculated with the electrodeposition bath form, the resin solid content in the electrodeposition bath was usually within 5% to 25% scope of the gross weight of aqueous dispersions.
Outside dewatering, water medium can contain a kind of agglomerated solvent.Useful agglomerated solvent comprises: hydrocarbon (class), alcohol (class), ester (class), ether (class) and ketone (class).Agglomerated solvent comprises preferably: alcohol (class), polyvalent alcohol and ketone.Concrete agglomerated solvent comprises: single ether, monobutyl ether and the monohexyl ether of Virahol, butanols, 2-Ethylhexyl Alcohol, isophorone, 4-methoxyl group-pentanone, ethylene glycol and propylene glycol and ethylene glycol.The amount of agglomerated solvent (based on water medium weight) generally between about 0.01% and 25%, is preferably about 0.05% to 5%.
In some example, the various additives that contain colorant composition in the dispersion liquid and when needing, add, for example surfactant, wetting agent, catalyzer, film for additive and enhancing coating flow and the additive of outward appearance (as in U.S. Patent No. 4,423, narrating in 166).Colorant composition may be the formation of usual type, for example, and oxide compound, strontium yellow, carbon black, coal dust, titanium dioxide, talcum, barium sulfate and the colored pigment (for example, cadmium yellow, cadmium red, chrome yellow and the like) of the oxide compound of iron, lead.In the dispersion liquid content of pigment usually with pigment to recently the expressing of resin, in enforcement of the present invention pigment to the ratio of resin usually within 0.02 to 1: 1 scope.Above mentioned in dispersion liquid the amount of other additive be about 0.01～20% of resin solid weight.
When above-mentioned aqueous dispersions was used for electrodeposition process, this aqueous dispersions was waited to be coated with surperficial conductive cathode as negative electrode with conductive anode and usefulness and is contacted.Along with the contacting of aqueous dispersions, when having applied enough voltage between electrode, on negative electrode, just deposit the film that adheres to of coating composition.The condition that galvanic deposit is implemented is similar to the condition of using in the galvanic deposit of other types of coatings in general.The voltage that is applied is variable, and for example, it can resemble 1 volt so low, also can be so high as thousands of volts, but be typically between 50 to 500 volts.The current density formation of insulation layer and lowering gradually between 0.5～5 ampere every square feet and in usually along with electrodeposition process.Coating composition of the present invention is applicable to various conductive substrates, the conductive carbon that particularly resembles metals such as steel, aluminium, copper, magnesium and scribble some material.
Coating (for example 90 °～260 ℃) baking about 1～40 minute and solidify at elevated temperatures behind the galvanic deposit coated.
The front mentions, of the present inventionly thisly is stable aqueous dispersions form through thionamic acid neutral cationic electrodepositable composition.It is than using typical organic acid, and for example the similar compositions of acetic acid and lactic acid neutralization has wonderful good throwing power.Throwing power means electrodeposition composition can deposit the essentially identical product of density on distance counter electrode different distance ability.Recommended the method for multiple measurement throwing power already, comprising Ford battery testing and General Motors Corporation's battery testing.For example referring to " coating technology magazines " such as Brewer (Journal of Paint Technology) 41 volumes, 535 phases, 461～471 pages, (1969); Gilchrist etc., american chemical association organic coating and plastic chemistry branch.Los Angeles meeting, (the 3-4 month in 1971) 31,1 phases of Preprint, 346～356 pages.
In addition, have found that in the cationic electrodeposition process, but in thionamic acid and resin passivation counter electrode or the anode crossed.Typical anode is made by stainless steel, has now found that to use the typical organic acid that resembles acetic acid or lactic acid can make anode dissolving lentamente in whole process in the cationic electrodeposition process.And the anodic dissolving has caused the bad and bad outward appearance of film quality.As a result, as enough big of this dissolving, then must change anode, the interruption of the electrodeposition process that causes thus is the fund of taking again consuming time.But through thionamic acid neutral resin purifying anode then.Be low that anode does not dissolve or its dissolved speed of similar system of classic relatively organic acid neutral resin is enough.
The following examples are in order to explanation the present invention, and should not regard qualification to details of the present invention as.Used deal and percentage composition among the embodiment and in the specification sheets except as otherwise noted, all represented with weight.
Embodiment
Following embodiment has explained the preparation of the various compositions that are used to prepare cation electrodeposition coating and the preparation of cation electrodeposition coating itself.Particularly prepare through thionamic acid neutral cationic electrodeposition resin and with it with compare with regard to its particle size through lactic acid and the similar cationic electrodeposition resin of acetic acid neutral.In addition, also the throwing power of cation electrodeposition coating product is carried out mutual comparison.Carrying out thionamic acid and lactic acid and acetic acid at last contrasts about the passivation anodic.
Embodiment A-C
These embodiment have explained the preparation of the various resin compositions that are used to prepare cation electrodeposition coating.
Embodiment A
Present embodiment has been explained when solidified coating the preparation that is added to the polyepoxide poly suboxygen alkyl diamine adducts of cationic electrodeposition in bathing for outward appearance preferably is provided subsequently.For preparing this adducts, its intermediate polyepoxide is made by the mixture of following composition:
The composition parts by weight
EPON828
[1]1000.0
Dihydroxyphenyl propane 308.1
Iodate Yi base triphenyl phosphonium 1.3
Butoxy ethanol 413.5
[1] diglycidyl ether of dihydroxyphenyl propane, about 188 epoxy equivalent (weight)s, Shell Chemical Co. produces
EPON828 and dihydroxyphenyl propane are placed reactor under nitrogen atmosphere, be heated to 100 ℃.Reaction mixture is maintained 110 ℃ until all dihydroxyphenyl propane dissolvings.So add iodate Yi base triphenyl phosphonium catalyzer, reaction mixture be heated to 160 ℃ of initiation reactions.Allow mixture heat release to 180 ℃.Then be cooled to 160 ℃.Keep this temperature one hour so that react completely.When the time comes, add butoxy ethanol, can obtain containing solid 76%.The product of epoxy equivalent (weight) 504 (based on solid).
And then prepare adducts by the mixture of following composition.
The composition parts by weight
JEFFAMINE D-2000 2362.2
Polyepoxide intermediate 1161.1 by above-mentioned preparation
Butoxy ethanol 308.5
The polyurethane linking agent
[1]3004.0
Acetic acid 63.2
Tensio-active agent 83.4
Deionized water 7478.7
[1] the polyurethane linking agent is to be made with the butoxy ethanol reaction by half end capped tolylene diisocyanate (2,4-/2,6-isomer mixture, isomer proportion are 80/20), products therefrom and TriMethylolPropane(TMP) is reacted with mol ratio at 3: 1 again.Linking agent is present in the cellosolvo solvent, wherein contains 72% solid.
[2] cats product, by 120 parts of alkyl imidazoline (GEIGY AMINE, available from Geigy Industrial Chemicals), (SURFYNOL 104 for 120 parts of alkynols, available from Air products and Chemicals, Inc.), 120 parts of butoxy ethanols and 17.9 parts of Glacial acetic acid mix and make.
Available from Jefferson Chemical Compan, commodity are called JEFFAMINE, D-2000, molecular weight is that the reaction of 2000 polyoxygenated propylene diamine and polyepoxide intermediate is as follows: under nitrogen atmosphere JEFFAMINE D-2000 is placed reactor, be heated to 90 ℃.With whole halfhour time adding polyepoxide intermediate and butoxy ethanol.Interpolation finishes, and reaction mixture is heated to 130 ℃, keeps this temperature and adds linking agent in 3 hours again.At 110 ℃, allow mixed with resin half an hour, be poured into then in the mixture of forming by acetic acid, tensio-active agent and deionized water and make resin dispersion.The gained reaction product contains solid 38.5%.
Embodiment B
A kind ofly be used to prepare pigment and grind of the mixture preparation of the quaternizing agent of vehicle by following composition:
The composition parts by weight
Half end capped toluene diisocynate
Own (alcohol) ester 320 of 2-ethyl
(in methyl iso-butyl ketone (MIBK), containing 95% solid)
Dimethylethanolamine 87.2
88% lactic acid aqueous solution 117.6
Butoxy ethanol 39.2
In suitable reactor, half oneself (alcohol) ester of end capped toluene diisocynate 2-ethyl is joined in the dimethylethanolamine under the room temperature.This mixture heat release is stirred mixture 1 hour at 80 ℃.After adding butoxy ethanol, place lactic acid.At 65 ℃, stirred reaction mixture one hour is to form required quaternizing agent.
Embodiment C
Pigment grinds the mixture preparation of vehicle by following composition:
The composition parts by weight
EPON829
[1]710.0
Dihydroxyphenyl propane 289.6
Half end capped vulcabond 406.0 of Embodiment B
Quaternary ammoniated dose 496.3 of Embodiment B
Deionized water 71.2
Butoxy ethanol 1205.6
[1] diglycidyl ether of dihydroxyphenyl propane, epoxy equivalent (weight) is about 188, available from Shell Chemical Co.
Under nitrogen atmosphere, EPON829 and dihydroxyphenyl propane are placed a suitable reactor, be heated to 150 °～160 ℃ beginning heat releases.Allow the reaction mixture heat release, keep 150 °～160 ℃ one hour.Reaction mixture is cooled to 120 ℃ then, adds own (alcohol) ester of half end capped toluene diisocynate 2-ethyl.After adding butoxy ethanol, 110 °～120 ℃ of the temperature maintenance of reaction mixture one hour.Reaction mixture is cooled to 85 ℃～90 ℃ then, stirs evenly, and charges into water after adding quaternary ammoniated dose.The temperature maintenance of reaction mixture is about 1 at 80 °～85 ℃ until acid number.
Embodiment D-F
These embodiment have represented to be used to prepare the various catalyst slurries and the pigment slurry of various cation electrodeposition coatings.
Embodiment D
Tributyltin oxide catalyst is scattered in the described grinding vehicle of Embodiment C, as following:
The composition parts by weight
Described in the Embodiment C 145
Pigment grinds vehicle
Deionized water 271.3
Dibutyl tin oxide 204.1
Above-mentioned each composition is mixed, in steel ball grinder, be ground to the fineness of Hegman No.7.
Embodiment E
The pigment that titanium dioxide, carbon black, lead silicate white and dibutyl tin oxide is dispersed in Embodiment C grinds in the vehicle, as following:
The composition parts by weight
Described in the Embodiment C 226.36
Pigment grinds vehicle
Deionized water 388.90
Titanium dioxide 564.31
Carbon black 16.54
Lead silicate 33.08
The catalyst slurry 87.38 of embodiment D
Successively above-mentioned each composition is mixed, in steel ball grinder, be ground to the fineness of Hegman No.7.
Embodiment F
The pigment that aluminum silicate clay, carbon black, lead silicate white and dibutyl tin oxide are scattered in Embodiment C grinds in the vehicle, as following:
The composition parts by weight
228.89 of Embodiment C
Pigment grinds vehicle
Deionized water 373.42
Aluminum silicate clay 311.24
Lead silicate 50.18
Carbon black 39.92
The catalyst slurry 103.21 of embodiment D
Above-mentioned composition is mixed in steel ball grinder grinding machine for grinding successively to the fineness of Hegman No.7.
Embodiment G
Present embodiment has represented to contain the preparation of the resin of epoxy group(ing) and amine mixt (secondary amine and contain the secondary amine mixture of ketoimine base).Reaction product neutralizes with lactic acid (embodiment G-1), acetic acid (embodiment G-2) and thionamic acid (embodiment G-3) and is dispersed in the water then.These dispersion systems are made comparisons by the size of particle size.This epoxy one polyimide resin reaction product is by the mixture preparation of following each composition.
The composition parts by weight
EPON828 2510.2
Dihydroxyphenyl propane-oxyethane 897.7
Adducts (mol ratio 1/6)
Dihydroxyphenyl propane 727.7
Methyl iso-butyl ketone (MIBK) 217.9
Benzyl dimethyl amine 3.5
Benzyl dimethyl amine 10.8
Linking agent
[1]3604.5
Two ketoimines
[2]285.2
N-Mono Methyl Ethanol Amine 241.8
1-phenoxy group-2-propyl alcohol 355.4
[1] the polyurethane linking agent is generated by half end capped tolylene diisocyanate (2,4/2,6-isomer mixture, isomer proportion are 80/20) and 2-hexyloxy ethanol.And with product and TriMethylolPropane(TMP) with mol ratio reaction in 3: 1.Linking agent contains 70% solid in methyl iso-butyl ketone (MIBK) and butanols (weight ratio 9: 1).
[2] two ketoimines are from diethylenetriamine and methyl iso-butyl ketone (MIBK) deutero-(containing 73% solid methyl iso-butyl ketone (MIBK)).
EPON828, dihydroxyphenyl propane-ethylene oxide adduct, dihydroxyphenyl propane and methyl iso-butyl ketone (MIBK) place a reactor, are heated to 140 ℃ under nitrogen atmosphere.Insert first part's benzyl dimethyl amine, allow about this reaction mixture heat release to 185 ℃, and reflux, the water of being deposited is all removed in the mode that generates azeotrope.Reaction mixture is cooled to 160 ℃, keeps half an hour, further is cooled to 145 ℃ again, adds second section benzyl dimethyl amine.This reaction maintains 145 ℃, until obtaining the low Gardner-Holdt viscosity of R-S.(in the 2-methoxypropanol, containing 50% resin solid this moment).At this moment, linking agent, two ketoimines and N-Mono Methyl Ethanol Amine succeedingly add.Allow the mixture heat release until 25 ℃ of stuck-at-s.After one hour 1-phenoxy group-2-propyl alcohol is joined in the resin compound, allow mixture mix 15 minutes at 125 ℃.Then resin is divided into three parts and disperses it with following method.
Embodiment G-1
The method of resin dispersion in water medium is: 2800 parts of resins are joined in the mixture of being made up of the cats product in 67.4 part 88% lactic acid aqueous solution, the 35.4 parts of embodiment A and 1294 parts of deionized waters.Further dilute this dispersion liquid with 2403 parts of deionized waters, vacuum take-off to be to remove organic solvent, can obtain solids content and be 35.1%, particle size is the dispersion liquid of 1670 dusts.
Embodiment G-2
The method of resin dispersion in water medium is: 2800 parts of resins are joined in the mixture of being made up of 39.6 parts of Glacial acetic acid, 35.4 parts of cats products and 1322 parts of deionized waters.Further dilute dispersion liquid with 2403 parts of deionized waters.Vacuum take-off can obtain having the dispersion liquid of 37.1% solids content and 1420 dust particle sizes to remove organic solvent.
Embodiment G-3
The method of resin dispersion in water medium is: 2800 parts of resins are joined in the mixture that is made of 64.0 parts of thionamic acids, 36.4 parts of cats products and 1416 parts of deionized waters.Further dilute this dispersion liquid with 2472 parts of deionized waters, re-use vacuum take-off, can obtain to have the dispersion liquid of the particle size of 35.8% solids content and 960 dusts to remove organic solvent.
Embodiment G-1 to G-3 shows: with thionamic acid neutral dispersive resin cation (R.C.) than having much smaller particle size with lactic acid and acetic acid neutral dispersive resin cation (R.C.).
Embodiment H
Present embodiment has been represented the acrylate copolymer of preparation amino-contained.This polymkeric substance neutralizes with lactic acid (embodiment H-1) and thionamic acid (embodiment H-2) and is scattered in the water.The particle size that compares dispersion liquid then.The acrylate copolymer of amino-contained is by the preparation of the mixture of following each composition:
The composition parts by weight
1-phenoxy group-2-propyl alcohol 236.2
Deionized water 18.2
Ethyl propenoate 616.0
Vinylbenzene 496.0
Rocryl 410 160.0
Methyl methacrylate 56.0
Glycidyl methacrylate 272.0
Uncle's dodecyl mercaptans 52.0
VAZO-67
[1]32.0
Mibk 11.2
1-phenoxy group-2-propyl alcohol 115.2
Deionized water 81.0
ARMEEN 2C
[2]65.9
Dimethylbenzene 36.2
N-Mono Methyl Ethanol Amine 122.6
Linking agent
[3]1086.1
Wherein [1] for from Du Pont company buy 2,2 '-azo two-(2-methylbutyronitrile)
[2] be Dicocoamine, available from Acker assistant chemical company, equivalent is 372
[3] be the polyurethane linking agent.It is to constitute by half end capped two isocyanic acid isophorones and ε-Ji Neixianan.This reaction product and TriMethylolPropane(TMP) were with 3: 1 molar ratio reactions, and linking agent contains 62% solid in mibk and cellosolvo (weight ratio 1: 3) solvent.
The 1-of first part phenoxy group-2-propyl alcohol (236.2 parts) and deionized water (18.2 parts) are placed a reactor.Place an erlenmeyer flask remix even ethyl propenoate, vinylbenzene, Rocryl 410, methyl methacrylate, glycidyl methacrylate, uncle's dodecyl mercaptans, VAZO-67, mibk and second section 1-phenoxy group-2-propyl alcohol.Get 10% monomer mixture and place this reactor, under nitrogen atmosphere, be heated, reflux about 100 ℃, with in the backflow mixture that was added drop-wise to reactor in 2.5 hours, the temperature of the reaction mixture of Hui Liuing rises to 116 ℃ during this period with remaining 90% monomer mixture.After monomer had added, the mixture in the reactor was kept half an hour at 116 ℃ again, then the second section water droplet is added in the reaction mixture, gathers overhead product simultaneously.In case whole water adds and finishes, continue heating and gather distillate, allowable temperature rises to 150 ℃.
Allow the finished product acrylate copolymer be cooled to 130 ℃.After adding the N-Mono Methyl Ethanol Amine, be added in the ARMEEN 2C of modulation pulping in the dimethylbenzene.Allow reaction mixture heat release to 145 ℃, be cooled to 125 °～130 ℃ again.Kept this temperature 2 hours.When the time comes, the material to 113 in the cooling reactor ℃ adds linking agent.This resin compound of fusion half an hour, be cooled to 75 ℃.With the resin separated into two parts, the following then method of showing is disperseed it:
Embodiment H-1
The method of resin dispersion in water medium is: 1500 parts of resins are joined in the mixture that 38.9 parts of aqueous solution that contain 88% lactic acid and 2891.5 parts of deionized waters form.Vacuum take-off can obtain containing 26.2% solid, the dispersion liquid of the particle size of 802 dusts to remove organic solvent.
Embodiment H-2
The method of resin dispersion in water medium is: 1500 parts of resins are added in the mixture of 36.9 parts of thionamic acids and 2903.5 parts of deionized water compositions.The vacuum take-off dispersion liquid obtains to contain the dispersion liquid of 27.1% solids content, 685 dust particle sizes to remove organic solvent.
Embodiment H-1 and H-2 show to have much smaller particle size with thionamic acid neutral dispersive resin cation (R.C.) than the dispersive resin cation (R.C.) with lactic acid neutralization.
Example I-V
These embodiment explain and use embodiment G-1, and 2,3 and H-1, some additive and slurry described in 2 resin cation (R.C.) and the front embodiment prepare cation electrodeposition coating.
Example I
Bathe as follows with embodiment G-1 through controlled cationic electrodeposition of reaction product preparation of lactic acid neutralization:
The composition parts by weight
The resin cation (R.C.) 1408.7 of embodiment G-1
The additive 185.6 of embodiment A
PARAPLEX WP-1
[1]36.3
Deionized water 1977.9
The pigment slurry 391.5 of embodiment E
Wherein [1] is propoxy-first (benzene) phenol of structure from Rohm and Haas company.
Above-mentioned additive, PARAPLEX WP-1 and small amount of deionized water (100 parts) at first mix, and mix resin cation (R.C.) again.Under agitation dilute formed mixture then, under agitation mix the pigment slurry again with remaining deionized water.Formed like this cation electrodeposition coating contains about 21% solid, and pigment is 0.3/1.0 to the ratio of tackiness agent.
Estimate as follows to formed bath.Bathing 83 (28 ℃) of temperature, under the voltage 275 laid shoot spares, the galvanic deposit 2 minutes in bath of phosphated (BONDERITE40) steel plate.Solidify this coating 30 minutes at 340 °F (177 ℃) then, measure the slickness and the thickness of coating.Under aforesaid coated and solidified condition, use GM throwing power battery, measure the GM throwing power.The results are shown in following table I.
The embodiment II
Use embodiment G-2 to prepare the roughly the same second kind of controlled cationic electrodeposition bath of embodiment I of all the other conditions through acetic acid neutral reaction product.This is bathed as example I, estimates with result listed in table 1.
The embodiment III
That uses embodiment G-3 carries out the roughly the same preparation of a kind of cationic electrodeposition bath of embodiment I and II of all the other conditions with thionamic acid neutral reaction product.This bath is estimated with the listed result of table 1 as the embodiment I.
The embodiment IV
The controlled cationic electrodeposition that the acrylate copolymer that contains amino with lactic acid neutralization of employing embodiment H-1 constitutes is bathed as follows:
The composition parts by weight
The resin cation (R.C.) 2135.1 of embodiment H-1
Deionized water 1663.9
The pigment slurry 201.0 of embodiment F
Under agitation dilute resin cation (R.C.), under agitation mix the pigment slurry again with deionized water.It is about 17% that the cationic electrodeposition that forms is bathed solids content, and pigment is 0.13: 1.0 to the ratio of tackiness agent.
The bath that forms is estimated as follows: bathing under temperature 83 (28 ℃) and the 275 volts of voltage galvanic deposit 2 minutes in bath of phosphated (BONDERITE40) steel plate.Descend solidified coating 20 minutes at 350 °F (177 ℃) then, measure the slickness and the thickness of coating.Adopt GM throwing power battery, under aforesaid coated and curingization condition, measure the GM throwing power.The results are shown in following table 1.
EXAMPLE V
That uses embodiment H-2 contains the cationic electrodeposition bath that the aminoacrylic acid polymer manufacture is analogous to embodiment 4 through the thionamic acid neutral.This bath is analogous to the following listed result of table 1 of embodiment 4 usefulness and estimates.
Table 1
The thickness of example I-V, slickness and throwing power
Embodiment disperses the state GM throwing power with the sorrel thick film
Sequence number (mil) (smooth or coarse) (inch)
I lactic acid 1.98 smooth 11-7/8
II acetic acid 1.90 smooth 12-1/4
III thionamic acid 1.93 smooth 12-7/8
IV lactic acid 0.98 smooth 11-1/8
V thionamic acid 0.96 smooth 13-1/2
For measuring thionamic acid, lactic acid and acetic acid corrosion effect, by the described preparation of synthesizing anolyte of following embodiment J-L to stainless steel anode.Experiment is 5 inches * 1 inch 316 stainless steel electrodes with anode, and they are inserted between two 5 inches * 1 inch 316 stainless steel cathodes.Electrode space is about 2 inches, and electrode 2 inches of the anolytes that submerge are dark.Experiment was switched on 4 hours under 1/2 ampere.The temperature maintenance of anolyte is about about 180 °F (82 ℃).Experimental result is the table II of face as follows.
Embodiment J
Every liter contains 8 millinormal thionamic acids, every liter of hydrogenchloride (60ppm Cl that contains 61.7 milligrams in deionized water
-) synthetic anolyte by the preparation of the mixture of following each composition:
Composition parts by weight (gram)
0.1N HCl 33.8
1% thionamic acid solution 155.4
Be diluted to 2 liters deionized water 1801.8
Embodiment K
Every liter contains 8 millinormal acetic acid, every liter and contains 61.7 milligrams of hydrogenchloride (60ppm Cl in deionized water
-) the synthetic anolyte of similar embodiment J by the preparation of the mixture of following each composition:
Composition parts by weight (gram)
0.1N HCl 33.8
1% acetum 96.0
Be diluted to 2 liters deionized water 1796.1
Embodiment L
Every liter contains the synthetic anolyte of similar embodiment J that 8 millinormal lactic acid, every liter contain 61.7 milligrams of hydrogenchloride (60ppm Cl) by the mixture preparation of following each composition in deionized water:
Composition parts by weight (gram)
0.1N HCl 33.8
1% contain 88% emulsion solution 163.6
Be diluted to 2 liters deionized water 1792.5
The table II
Anodic dissolution rate in the embodiment J-L anolyte
The anolyte anodic dissolution rate
Embodiment acid (mils per year)
J thionamic acid 29.6
K acetic acid 5498
L lactic acid 6317
Wherein [1] is measured according to ASTM D-A262.
The result of the foregoing description shows: the anolyte that contains acetic acid and lactic acid is very big to the solvency action of stainless steel anode.And thionamic acid shows its passivation anodic effect with extremely low anodic dissolution rate.
Claims (10)
1, contain the cationic electrodepositable composition of the resin phase that is dispersed in the water medium, the pH value of described composition is at least 5, and it contains less than 2, the lead of 000ppm, and described resin has the basic nitrogen group mutually, and it neutralizes through the acid of following formula at least in part:
R is H or C in the formula
1-C
4Alkyl.
2,, wherein saidly account for 2% to 60% of electrodeposition composition gross weight mutually through the dispersive resin according to the cationic electrodepositable composition of claim 1.
3, the composition of claim 1, it contains the primary amine group as the basic nitrogen group.
4, according to the composition of claim 1, wherein said resin is the reaction product that contains epoxy and primary amine or secondary amine mutually.
5, composition according to claim 3, wherein resin is epoxy-containing yl resin and the reaction product that contains the secondary amine of ketoimine group mutually.
6, composition according to claim 1, resin wherein are mutually for containing amino acrylate copolymer.
7, composition according to claim 1, it also contains a kind of end capped isocyanate curing agent.
8, a kind of coated is as the method for the conductive substrates of negative electrode in the circuit, this method comprises that described negative electrode and anode are immersed in the cationic electrodeposition composition solution, also be included in and pass through electric current between described anode and the negative electrode, electrodeposition composition is coated with as one is deposited upon on the negative electrode.The method is characterized in that electrodeposition composition is the composition of claim 1.
9, method according to Claim 8, wherein said cationic electrodeposition composition are the compositions of claim 4.
10, method according to Claim 8, wherein said cationic electrodeposition composition are the compositions of claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/248,680 US4933056A (en) | 1988-09-26 | 1988-09-26 | Cationic electrodepositable compositions through the use of sulfamic acid and derivatives thereof |
| US248,680 | 1988-09-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1041376A true CN1041376A (en) | 1990-04-18 |
| CN1016437B CN1016437B (en) | 1992-04-29 |
Family
ID=22940206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89106745A Expired CN1016437B (en) | 1988-09-26 | 1989-09-02 | Improved cationic electrodepositable compositions through use of sulfamic acid and derivatives thereof |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4933056A (en) |
| EP (1) | EP0361882B1 (en) |
| JP (1) | JPH0689274B2 (en) |
| KR (1) | KR930005540B1 (en) |
| CN (1) | CN1016437B (en) |
| AR (1) | AR246543A1 (en) |
| AU (1) | AU595150B1 (en) |
| BR (1) | BR8901963A (en) |
| CA (1) | CA1334714C (en) |
| DE (1) | DE68913886T2 (en) |
| ES (1) | ES2052927T3 (en) |
| MX (1) | MX164740B (en) |
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| CN100523044C (en) * | 2003-12-11 | 2009-08-05 | 威士伯来源有限公司 | Blocked isocyanate crosslinker solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU350376A1 (en) * | 1970-10-05 | 1973-08-28 | В. М. Пол кова, Ю. Ф. Дейнега, Н. В. Власюк, С. А. Жабицка Институт коллоидной химии , химии воды Украинской ССР | METHOD OF COATING |
| US4419467A (en) * | 1981-09-14 | 1983-12-06 | Ppg Industries, Inc. | Process for the preparation of cationic resins, aqueous, dispersions, thereof, and electrodeposition using the aqueous dispersions |
| DE3422509A1 (en) * | 1984-06-16 | 1985-12-19 | Basf Ag, 6700 Ludwigshafen | COATING AGENTS, THEIR PRODUCTION AND USE |
| US4677168A (en) * | 1985-03-29 | 1987-06-30 | Hoy Kenneth L | Water borne high solids coating compositions |
| JPS6341570A (en) * | 1986-08-06 | 1988-02-22 | Nippon Paint Co Ltd | Electrodeposition coating composition |
-
1988
- 1988-09-26 US US07/248,680 patent/US4933056A/en not_active Expired - Lifetime
-
1989
- 1989-04-07 CA CA000596106A patent/CA1334714C/en not_active Expired - Lifetime
- 1989-04-26 BR BR898901963A patent/BR8901963A/en not_active IP Right Cessation
- 1989-06-06 AU AU36093/89A patent/AU595150B1/en not_active Expired
- 1989-08-14 MX MX17191A patent/MX164740B/en unknown
- 1989-09-02 CN CN89106745A patent/CN1016437B/en not_active Expired
- 1989-09-22 AR AR89314983A patent/AR246543A1/en active
- 1989-09-25 KR KR1019890013761A patent/KR930005540B1/en not_active Expired - Lifetime
- 1989-09-26 DE DE68913886T patent/DE68913886T2/en not_active Expired - Lifetime
- 1989-09-26 ES ES89309813T patent/ES2052927T3/en not_active Expired - Lifetime
- 1989-09-26 JP JP1250412A patent/JPH0689274B2/en not_active Expired - Lifetime
- 1989-09-26 EP EP89309813A patent/EP0361882B1/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074027C (en) * | 1998-04-09 | 2001-10-31 | 化工部常州涂料化工研究院 | Preparation of resin emulsion for electrophoretic paint used on thick-film cathode |
| CN100523044C (en) * | 2003-12-11 | 2009-08-05 | 威士伯来源有限公司 | Blocked isocyanate crosslinker solution |
Also Published As
| Publication number | Publication date |
|---|---|
| DE68913886T2 (en) | 1994-10-06 |
| EP0361882B1 (en) | 1994-03-16 |
| EP0361882A3 (en) | 1992-03-11 |
| ES2052927T3 (en) | 1994-07-16 |
| US4933056A (en) | 1990-06-12 |
| BR8901963A (en) | 1990-04-10 |
| CA1334714C (en) | 1995-03-07 |
| JPH02127481A (en) | 1990-05-16 |
| JPH0689274B2 (en) | 1994-11-09 |
| DE68913886D1 (en) | 1994-04-21 |
| EP0361882A2 (en) | 1990-04-04 |
| AU595150B1 (en) | 1990-03-22 |
| CN1016437B (en) | 1992-04-29 |
| KR900004888A (en) | 1990-04-13 |
| KR930005540B1 (en) | 1993-06-23 |
| MX164740B (en) | 1992-09-21 |
| AR246543A1 (en) | 1994-08-31 |
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